US11891536B2 - Coating, injection needle and method for manufacturing the same - Google Patents

Coating, injection needle and method for manufacturing the same Download PDF

Info

Publication number
US11891536B2
US11891536B2 US17/533,407 US202117533407A US11891536B2 US 11891536 B2 US11891536 B2 US 11891536B2 US 202117533407 A US202117533407 A US 202117533407A US 11891536 B2 US11891536 B2 US 11891536B2
Authority
US
United States
Prior art keywords
slurry
group
alkyl
tube
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US17/533,407
Other versions
US20220169891A1 (en
Inventor
Wei Wang
Bo-Ling Xu
Xiao-Qing Fu
Li-Li Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fulian Yuzhan Precision Technology Co Ltd
Original Assignee
Fulian Yuzhan Precision Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fulian Yuzhan Precision Technology Co Ltd filed Critical Fulian Yuzhan Precision Technology Co Ltd
Assigned to SHENZHENSHI YUZHAN PRECISION TECHNOLOGY CO., LTD. reassignment SHENZHENSHI YUZHAN PRECISION TECHNOLOGY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FU, Xiao-qing, WANG, WEI, XU, Bo-ling, ZHANG, Li-li
Assigned to FULIAN YUZHAN PRECISION TECHNOLOGY CO.,LTD reassignment FULIAN YUZHAN PRECISION TECHNOLOGY CO.,LTD CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SHENZHENSHI YUZHAN PRECISION TECHNOLOGY CO., LTD.
Publication of US20220169891A1 publication Critical patent/US20220169891A1/en
Application granted granted Critical
Publication of US11891536B2 publication Critical patent/US11891536B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/146—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies to metallic pipes or tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • B05D7/225—Coating inside the pipe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C17/00—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces
    • B05C17/005—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces for discharging material from a reservoir or container located in or on the hand tool through an outlet orifice by pressure without using surface contacting members like pads or brushes
    • B05C17/00503—Details of the outlet element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes

Definitions

  • the subject matter herein generally relates to coating, and more particularly, relates to a coating, an injection needle and a method for manufacturing the coating applied on the injection needle.
  • Products may be assembled from multiple parts. Different parts can be assembled together such as by welding, injection molding, or bonding. When different parts are assembled together by bonding, adhesive is first applied on one part, and then the other parts are pressed on the adhesive, so that the parts are joined together by the adhesive.
  • the adhesive is usually applied on the part through an injection needle. However, the injection needle may be blocked by the adhesive, resulting in a short service life and frequent replacement of the injection needle, decreasing productivity and increasing cost.
  • a coating applied on a tube for transporting adhesive, a material of the coating includes polysiloxane.
  • the polysiloxane includes a first monomer unit and a second monomer unit.
  • the first monomer unit includes at least one selected from a group consisting of —O—Si—(R 1 )(R 2 )(R 3 ), Si—(R 1 )(R 2 )(—O—) 2 , and Si—(R 1 )(—O—) 3 .
  • the second monomer unit includes Si(—O—) 4 .
  • the R 1 , R 2 and R 3 are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
  • the R 1 , R 2 and R 3 are independently selected from alkyl with not more than four carbon atoms.
  • At least one of the R 1 , R 2 and R 3 is selected from fluoroalkyl.
  • the tube is made of stainless steel; and the coating is bonded to the tube through a chemical bond of —O—.
  • a thickness of the coating is in the range of 0.1 ⁇ m to 2 ⁇ m.
  • a surface roughness of the coating is in the range of 2 nm to 100 nm.
  • a bonding force between the tube and the coating is at least 4 B under a cross-cut test.
  • An injection needle applied to transporting adhesive includes a tube and a coating.
  • the coating is formed on the inner surface of the tube.
  • the material of the coating comprises polysiloxane.
  • the polysiloxane comprises a first monomer unit and a second monomer unit.
  • the first monomer unit comprises at least one group selected from the group consisting of —O—Si—(R 1 )(R 2 )(R 3 ), Si—(R 1 )(R 2 )(—O—) 2 , and Si—(R 1 )(—O—) 3 .
  • the second monomer unit comprises Si(—O—) 4 .
  • the R 1 , R 2 and R 3 groups are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
  • the R 1 , R 2 and R 3 are independently selected from alkyl with not more than four carbon atoms.
  • At least one group of the R 1 , R 2 and R 3 is selected from fluoroalkyl.
  • the tube is made of stainless steel; and the coating is bonded to the tube through a chemical bond of —O—.
  • a thickness of the coating is in the range of 0.1 ⁇ m to 2 ⁇ m.
  • a surface roughness of the coating is in the range of 2 nm to 100 nm.
  • a bonding force between the tube and the coating is at least 4 B under a cross-cut test.
  • a method for manufacturing a coating applied on an injection needle for transporting adhesive comprising a tube.
  • the method comprises: applying a hydroxylation treatment on the tube to form hydroxyl groups on an inner surface of the tube; immersing the tube in a slurry; wherein the slurry comprises a first monomer and a second monomer, the first monomer is selected from a silane containing at least one alkoxy and at least one alkyl, and the second monomer is selected from a silicate ester; applying a leveling treatment on the slurry adhered to the inner surface of the tube; and curing the slurry to form the coating on the inner surface of the tube.
  • the alkyl in the silane and the alkyl in the silicate ester are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl;
  • the silane comprises at least one selected from the group consisting of monosilane and bisilane;
  • the silicate ester comprises at least one selected from the group consisting of monosilate ester and bisilate ester.
  • the alkyl group in the silane and the alkyl group in the silicate are independently selected from alkyl with not more than four carbon atoms.
  • At least one of the alkyl in the silane and the alkyl in the silicate is selected from fluoroalkyl.
  • a material of the tube comprises stainless steel
  • the step of applying a hydroxylation treatment on the tube comprises: applying a plasma treatment in an air atmosphere to form hydroxyl groups on the tube; wherein a power of a plasma treatment machine in the plasma treatment is in the range of 100 W to 1000 W, and a time period of the plasma treatment is in the range of 0.5 min to 10 min.
  • an angle for leveling treatment applied on the slurry is in the range of 45 degrees to 90 degrees.
  • a time period of leveling treatment applied on the slurry is in the range of 0.1 h to 1 h.
  • a temperature for curing the slurry is in the range of 70 degrees Celsius to 80 degrees Celsius.
  • a time period for curing the slurry is in the range of 2 h to 6 h.
  • the outermost surface of the coating is composed of alkyl.
  • the alkyl has excellent chemical stability, and do not react with the adhesive, thus effectively increase the service life of the injection needle.
  • the method for manufacturing the coating applied on the injection needle in the disclosure the raw materials are silane and silicate, and these raw materials are easily available, which is beneficial to reduce production costs.
  • the method for manufacturing the coating has low requirements for equipment.
  • the coating can be mass-produced.
  • the method for manufacturing the coating also reduces the preparation cost, the reaction temperature is low, and the plastic will not be affected.
  • FIG. 1 illustrates simplified cross-sectional side view of an injection needle, in accordance with some embodiments of the present disclosure.
  • FIG. 2 illustrates a flowchart of a method for manufacturing an injection needle, in accordance with some embodiments of the present disclosure.
  • an injecting needle 100 is provided.
  • the injecting needle 100 includes a coating 10 and a tube 20 .
  • the coating 10 is applied on an inner surface of the tube 20 for transporting an adhesive.
  • the tube 20 is made of stainless steel.
  • the coating 10 prevents the tube 20 from being blocked by the adhesive.
  • a diameter of the tube 20 is not limited. In some embodiments, the diameter of the tube 20 is small, such as needle-size; in some embodiments, the diameter of the tube 20 is large.
  • the coating 10 is made of polysiloxane.
  • the polysiloxane includes a first monomer unit and a second monomer unit.
  • the first monomer unit is at least one selected from the group consisting of —O—Si—(R 1 )(R 2 )(R 3 ), Si—(R 1 )(R 2 )(—O—) 2 , and Si—(R 1 )(—O—) 3 .
  • the second monomer unit contains Si(—O—) 4 .
  • the polysiloxane is formed by a polymerization of silane compound containing at least one consisting of the R 1 , R 2 , and R 3 .
  • the R 1 , R 2 and R 3 are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
  • a chemical stability of the alkyl is high.
  • the coating 10 does not react with the tube 20 or the adhesive, so as to prevent the adhesive from blocking the tube 20 and improve a service life of the injection needle 100 .
  • the R 1 , R 2 and R 3 are independently selected from alkyl with not more than four carbon atoms.
  • the alkyl is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.
  • At least one of the R 1 , R 2 and R 3 can be fluoroalkyl. That is, at least one hydrogen atom in the R 1 , R 2 and R 3 is replaced by a fluorine atom.
  • the fluorine atom increases a wear resistance of the coating 10 , thereby improving the service life of the injection needle 100 .
  • the coating 10 is applied on the tube 20 after hydroxylation treatment, and the coating 10 is bonded to the tube 20 through a chemical bond of —O—, thus, a bonding force between the tube 20 and the coating 10 is strong.
  • the bonding force between the tube 20 and the coating 10 is at least 4B under a cross-cut test.
  • a thickness of the coating 10 is about in the range of 0.1 ⁇ m to 2 ⁇ m. If the thickness of the coating 10 is too thick, the coating 10 will be hard to solidify, and the stress of the coating will be high. Small crack may appear on the coating due the high stress. The adhesive may stick on the surface with small crack, which will cause the tube 20 blocked by the sticking adhesive, which reduces the service life of the injection needle 100 . If the thickness of the coating 10 is too thin, the coating 10 cannot fully cover the inner surface of the tube 20 , due to the adhesive having higher binding force with the rough surface than with the smooth surface, the adhesive will stick on the surface without coating 10 to block the tube 20 , which also reduces the service life of the injection needle 100 .
  • a surface roughness of the coating 10 is about in the range of 2 nm to 100 nm.
  • a method for manufacturing the coating 10 inside a tube 20 is also provided.
  • the injection needle 100 includes the tube 20 .
  • the tube 20 is made of stainless steel.
  • the method for manufacturing the injection needle 100 includes following steps.
  • Step S 1 applying a hydroxylation treatment on the tube 20 to form hydroxyl groups on an inner surface of the tube 20 .
  • the step S 1 can be carried out by applying a plasma treatment in an air atmosphere to form hydroxyl groups on the tube 20 .
  • the plasma treatment is applied in oxygen atmosphere to quickly form the hydroxyl groups on the tube 20 .
  • the hydroxyl groups increase an electrical polarity of the tube 20 , which is conducive to adhesion of the coating 10 and increases the bonding force between the tube 20 and the coating 10 .
  • the tube 20 is combined with another tube which made of plastic.
  • a needle holder containing stainless steel can be placed at one end of a syringe made of plastic.
  • a power of a plasma treatment machine in the plasma treatment is about in the range of 100 W to 1000 W, and a time period of the plasma treatment is about in the range of 0.5 min to 10 min. The power and the time period of the plasma treatment cannot be too high or too long, either one may cause the plastic deformed.
  • Step S 2 immersing the tube 20 in a slurry.
  • the slurry includes a first monomer and a second monomer.
  • the first monomer is selected from silane containing at least one alkoxy and at least one alkyl
  • the second monomer is selected from silicate ester.
  • the alkyl in the silane and the alkyl in the silicate ester are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
  • the silane includes at least one selected from the group consisting of monosilane and bisilane.
  • the silicate ester includes at least one selected from the group consisting of monosilate ester and bisilate ester.
  • a formula of the silane may include, but is not limited to at least one of R 4 O—Si—(R 1 )(R 2 )(R 3 ), R 4 O—Si—(R 1 )(R 2 )(—OR 3 ), R 4 O—Si—(R 1 )(—OR 2 )(—OR 3 ), (R 1 )(R 2 )(R 3 )—Si—O—Si—(R 4 )(R 5 )(R 6 ), and (R 1 )(R 2 )(R 3 )—Si—R 4 —Si—(OR 5 )(R 6 )(R 7 ).
  • a formula of the silicate ester can be selected from at least one of (R 8 O—)(R 9 O—)Si(—OR 10 )(—OR 11 ), and (R 8 O)(R 9 O)(R 10 O)—Si—O—Si—(OR 11 )(OR 12 )(OR 13 ).
  • the first monomer is cross-linked with the second monomer. Specifically, the alkoxy of the first monomer reacts to form a group of
  • the alkoxy of the second monomer reacts to form a group of
  • the networked structure contains polysiloxane of at least one monomer unit of —O—Si—(R 1 )(R 2 )(R 3 ), —O—Si—(R 1 )(R 2 )(—O—), —O—Si—(R 1 )(—O—) 2 , and —O—Si(—O—) 3 .
  • the first alkyl connected to silicon in the first monomer is disposed on the outermost layer of the formed polysiloxane. The first alkyl is in contact with the adhesive in the tube 20 .
  • the adhesive is mostly a molecule containing a polar group
  • the first alkyl is alkyl, which is a non-polar molecular.
  • the intermolecular force between the first alkyl and the binder is relatively weak.
  • the first alkyl provides toughness to the coating 10
  • the first alkyl also provides non-stick properties between the finished coating 10 and the adhesive it carries.
  • the second monomer is hydrolyzed, a glass-like structure is formed, which provides the coating 10 with a smoothness similar to that of inorganic substances, thereby preventing the coating 10 and the adhesive from being strongly bonded and causing the tube 20 to be blocked.
  • the first monomer should not be too much, otherwise it will cause the coating 10 to be too elastic, which is not conducive to the transporting of adhesive.
  • a percentage content of the second monomer should not be too much, otherwise it will cause the coating 10 to be too crisp or brittle, and then the coating 10 might crack due to internal stresses during the drying process.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 in silane and the R 8 , R 9 , R 10 , R 11 , R 12 , R 13 in the silicate esters all represent alkyl.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and the R 8 , R 9 , R 10 , R 11 , R 12 , R 13 may be the same or different.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 merely distinguish between the first alkyl and the second alkyl in the silanes and the alkyl in the silicate esters.
  • the alkyl in the silane (including the first alkyl and the second alkyl) and the alkyl in the silicate are independently selected from alkyl with not more than four carbon atoms.
  • the alkyl has small steric hindrance, which is beneficial to the reaction between the first monomer and the second monomer.
  • At least one of the alkyl in the silane (including the first alkyl and the second alkyl) and the alkyl in the silicate is selected from fluoroalkyl.
  • the first alkyl is formed in the coating 10 , and the fluoroalkyl increases a wear resistance and hydrophobicity of the coating 10 , thereby increasing the service life of the injection needle 100 .
  • the fluoroalkyl connected to oxygen increases the polarity of the first monomer and the second monomer, and is beneficial to the removal of the second alkyl and the alkyl in the second monomer, thereby facilitating the formation of a networked structure.
  • ultrasonic treatment and vacuuming steps can also be added to promote uniform distribution of the slurry on the tube 20 .
  • the slurry may include at least one of film-forming agent, viscosity regulator, dispersant, leveling agent, catalyst, and activator.
  • a mass ratio of the film-forming agent in the slurry is about in the range of 1% to 15%. According to some embodiments, the mass ratio of the film-forming agent in the slurry is one of 2.5%, 5.6%, 8.0%, 11.5%, and 13.9%.
  • the film-forming agent is at least one selected from the group consisting of dimethylsilanol, polymethylsilanetriol, tetraethyl orthosilicate, methyltriethoxysilane, dimethyldiethylsilane, ethyltrimethoxysilane, ethane-1,2-diylbis(methylsilane), 3-(aminopropyl)triethoxysilane (KH550) and 3-methacryloxypropyltrimethoxysilane (KH570).
  • the addition of the film-forming agent allows the slurry to quickly form film to form a coating 10 .
  • the film-forming agent is at least two selected from the group consisting of Tetraethyl orthosilicate, methyltriethoxysilane, dimethyldiethylsilane, ethyltrimethoxysilane and ethane-1,2-diylbis(methylsilane).
  • the selection of the film-forming agent that is, the selection range of the first monomer and/or the second monomer.
  • a mass ratio of the viscosity regulator in the slurry is about in the range of 10% to 20%. According to some embodiments, the mass ratio of the viscosity regulator in the slurry is one of 12.3%, 14.2%, 16.0%, 17.8%, and 19.1%.
  • the viscosity regulator is at least one selected from the group consisting of ethyl acetate, isopropyl acetate, ethylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and dipropylene glycol ethyl ether acetate.
  • the viscosity regulator adjusts the viscosity of the slurry.
  • the viscosity regulator is at least two selected from the group consisting of ethyl acetate, isopropyl acetate, di(propylene glycol) methyl ether acetate and dipropylene glycol methyl ether acetate.
  • a mass ratio of the dispersant in the slurry is about in the range of 1% to 9%. According to some embodiments, the mass ratio of the dispersant in the slurry is one of 2.5%, 3.6%, 5.6%, 7.0%, and 7.5%.
  • the dispersant is at least one selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, and isobutanol.
  • the dispersant reduces a force between the components of the slurry and facilitates the dispersion and spreading of the slurry.
  • the dispersant is at least two selected from the group consisting of methanol, ethanol and isopropanol.
  • a mass ratio of the leveling agent in the slurry is about in the range of 55% to 90%. According to some embodiments, the mass ratio of the leveling agent in the slurry is one of 60%, 66%, 70%, 73%, and 85%.
  • the leveling agent is at least one selected from the group consisting of 2-methoxyethanol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, 1-ethoxy-2-propanol, and dipropylene glycol ethyl ether.
  • the leveling agent reduces an interfacial tension of the slurry and facilitates infiltration between the slurry and the tube 20 .
  • the leveling agent is at least two selected from the group consisting of diethylene glycol monomethyl ether, 1-methoxy-2-propanol, and 2-ethoxyethanol.
  • a mass ratio of the catalyst in the slurry is about in the range of 0.02% to 2%. According to some embodiments, the mass ratio of the catalyst in the slurry is one of 0.10%, 0.52%, 0.85%, 1.28%, and 1.67%.
  • the catalyst is at least one selected from the group consisting of formic acid, acetic acid, hydrochloric acid, and hydrofluoric acid.
  • the catalyst accelerates the reaction of the first monomer and the second monomer.
  • a mass ratio of the activator in the slurry is about in the range of 0.5% to 5%. According to some embodiments, the mass ratio of the activator in the slurry is one of 0.8%, 1.5%, 2.8%, 3.6%, and 4.5%.
  • the activator is water.
  • the activator hydrolyses the first monomer and the second monomer, so that a crosslinking reaction occurs.
  • Step S 3 applying a leveling treatment on the slurry adhered to the inner surface of the tube 20 , so that the surface roughness of the coating 10 is smoothed, which can be about in the range of 2 nm to 100 nm.
  • the surface roughness of the coating 10 should not be too great, which would hinder a flow of the adhesive.
  • An angle for leveling treatment applied on the slurry is about in the range of 45 degrees to 90 degrees.
  • a time period of leveling treatment applied on the slurry is about in the range of 0.1 h to 1 h.
  • the time period of the leveling treatment is one of 0.2 h, 0.4 h, 0.6 h, 0.8 h, and 0.9 h.
  • Step S 4 curing the slurry to form the injection needle 100 with the coating 10 on the inner surface of the tube 20 .
  • a temperature for curing the slurry is about in the range of 70 degrees Celsius to 80 degrees Celsius. According to some embodiments, the temperature is one of 72 degrees Celsius, 74 degrees Celsius, 76 degrees Celsius, and 78 degrees Celsius.
  • a time period for curing the slurry is about in the range of 2 h to 6 h. According to some embodiments, the time period is one of 2.6 h, 3.3 h, 4.2 h, 4.9 h, and 5.4 h.
  • the material of the tube 20 contains stainless steel, and the tubes are all needles.
  • a hydroxylated injection needle was immersed in the slurry including the first monomer and the second monomer.
  • the first monomer was methyltriethoxysilane.
  • the mass ratio of methyltriethoxysilane in the slurry was 0.3%.
  • the second monomer was tetramethyl orthosilicate.
  • the mass ratio of tetramethyl orthosilicate in the slurry was 5%.
  • the slurry was leveled, the slurry was cured to form a coating on the inner surface of the injection needle.
  • the contact angle of the coating was 100 degrees.
  • the injection needle with the coating continuously transports adhesive, and the service life of the injection needle was 38 h.
  • Example 2 A difference from the Example 1 was that the first monomer was triethoxyisobutylsilane, the mass ratio of triethoxyisobutylsilane in the slurry was 0.6%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 5% in Example 2.
  • the contact angle of the coating was 88 degrees.
  • the service life of the injection needle was 46 h.
  • Example 3 A difference from the Example 1 was that the first monomer was propyltriethoxysilane, the mass ratio of propyltriethoxysilane in the slurry was 0.4%; and the second monomer was tetraisopropyl orthosilicate, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 8% in Example 3.
  • the contact angle of the coating was 84 degrees.
  • the service life of the injection needle was 36 h.
  • Example 4 A difference from the Example 1 was that the first monomer was 1,2-bis(triethoxysilyl)ethane, the mass ratio of 1,2-bis(triethoxysilyl)ethane in the slurry was 0.5%; and the second monomer was tetrabutylorthosilicate, and the mass ratio of tetrabutylorthosilicate in the slurry was 7% in Example 4.
  • the contact angle of the coating was 79 degrees.
  • the service life of the injection needle was 34 h.
  • Example 5 A difference from the Example 1 was that the first monomer was trimethoxy(propyl)silane, and the mass ratio of trimethoxy(propyl)silane in the slurry was 0.5%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 5% in Example 5.
  • the contact angle of the coating was 87 degrees.
  • the service life of the injection needle was 48 h.
  • Example 6 A difference from the Example 1 was that the first monomer was diethoxydimethylsilane, the mass ratio of diethoxydimethylsilane in the slurry was 0.7%; and the second monomer was tetraisopropyl orthosilicate, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 7% in Example 6.
  • the contact angle of the coating was 75 degrees.
  • the service life of the injection needle was 50 h.
  • Example 7 A difference from the Example 1 was that the first monomer was methoxy(trimethyl)silane, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.2%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 4% in Example 7.
  • the contact angle of the coating was 92 degrees.
  • the service life of the injection needle was 46 h.
  • Example 8 A difference from the Example 1 was that the first monomer was methyltriethoxysilane and methoxy(trimethyl)silane, the mass ratio of methyltriethoxysilane in the slurry was 1%, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.5%; and the second monomer was tetraethyl orthosilicate and tetramethyl orthosilicate, the mass ratio of tetraethyl orthosilicate in the slurry was 3%, the mass ratio of tetramethyl orthosilicate in the slurry was 3% in Example 8.
  • the contact angle of the coating was 106 degrees.
  • the service life of the injection needle was 40 h.
  • Example 9 A difference from the Example 1 was that the first monomer was isobutyltriethoxysilane and diethoxydimethylsilane, the mass ratio of isobutyltriethoxysilane in the slurry was 0.5%, the mass ratio of diethoxydimethylsilane in the slurry was 1%; and the second monomer was tetraethyl orthosilicate and tetraisopropyl orthosilicate, the mass ratio of tetraethyl orthosilicate in the slurry was 4%, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 1% in Example 9.
  • the contact angle of the coating was 98 degrees.
  • the service life of the injection needle was 50 h.
  • Example 10 A difference from the Example 1 was that the first monomer was methyltriethoxysilane, methoxy(trimethyl)silane and trimethoxy(propyl)silane, the mass ratio of methyltriethoxysilane in the slurry was 0.5%, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.5%, and the mass ratio of trimethoxy(propyl)silane in the slurry was 1%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 6% in Example 10.
  • the contact angle of the coating was 90.
  • the service life of the injection needle was 54 h.
  • Example 1 A difference from the Example 1 was that the monomer was (3-glycidyloxypropyl)trimethoxysilane, the mass ratio of (3-glycidyloxypropyl)trimethoxysilane in the slurry was 5% in Comparative Example 1.
  • the contact angle of the coating was 60 degrees.
  • the service life of the injection needle was 5 h.
  • Example 2 A difference from the Example 1 was that the monomer was (aminopropyl)triethoxysilane, the mass ratio of (aminopropyl)triethoxysilane in the slurry was 6% Comparative Example 2.
  • the contact angle of the coating was 70 degrees.
  • the service life of the injection needle was 5 h.
  • Example 3 A difference from the Example 1 was that the monomer was vinyltrimethoxysilane, the mass ratio of vinyltrimethoxysilane in the slurry was 3% Comparative Example 3.
  • the contact angle of the coating was 65 degrees.
  • the service life of the injection needle was 6 h.
  • Comparing the test results of Examples 1 to 10 and Comparative Examples 1 to 3 clearly shows that the contact angles of the injection needles with the coating made in Examples 1 to 10 are larger than those of Comparative Examples 1 to 3, which prevents the adhesive from sticking to the tube. Compared with Comparative Examples 1 to 3, the service life of the injection needles made in Examples 1 to 10 was greatly improved, and service life was 7 to 10 times that of Comparative Examples 1 to 3.
  • the surface of the coating was alkyl with good chemical stability, and alkyl does not react with the adhesive, thereby effectively increasing the service life of the injection needle.
  • the outermost surface of the coating is composed of alkyl.
  • the alkyl has excellent chemical stability, and do not react with the adhesive, thus effectively increase the service life of the injection needle.
  • the method for manufacturing the coating in the disclosure the raw materials are silane and silicate, and these raw materials are easily available, which is beneficial to reduce production costs.
  • the method for manufacturing the coating has low requirements for equipment.
  • the coating can be mass-produced.
  • the method for manufacturing the coating also reduces the preparation cost, the reaction temperature is low, and the plastic will not be affected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

A non-stick, durable, and long-serving coating in an inner surface of a tube that transports adhesive, a material of the coating includes polysiloxane. The polysiloxane includes a first monomer unit and a second monomer unit. The first monomer unit is at least one group selected from the group consisting of —O—Si—(R1)(R2)(R3), Si—(R1)(R2)(—O—)2, and Si—(R1)(—O—)3, the R1, R2 and R3 being independently selected from the group consisting of substituted alkyl and unsubstituted alkyl. The second monomer unit includes Si(—O—)4. An injection needle and a method for manufacturing the coating on an injection needle is also provided.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims all benefits accruing under 35 U.S.C. § 119 from Chinese Patent Application No. 202011402400.7, filed on Dec. 2, 2020, in the State Intellectual Property Office of China, the entire contents of which are incorporated herein by reference.
FIELD
The subject matter herein generally relates to coating, and more particularly, relates to a coating, an injection needle and a method for manufacturing the coating applied on the injection needle.
BACKGROUND
Products may be assembled from multiple parts. Different parts can be assembled together such as by welding, injection molding, or bonding. When different parts are assembled together by bonding, adhesive is first applied on one part, and then the other parts are pressed on the adhesive, so that the parts are joined together by the adhesive. The adhesive is usually applied on the part through an injection needle. However, the injection needle may be blocked by the adhesive, resulting in a short service life and frequent replacement of the injection needle, decreasing productivity and increasing cost.
SUMMARY
In view of the above situation, it is necessary to provide a coating, an injection needle and a method for manufacturing the coating applied on the injection needle to solve at least one of the above-mentioned problems.
According to some embodiments, a coating applied on a tube for transporting adhesive, a material of the coating includes polysiloxane. The polysiloxane includes a first monomer unit and a second monomer unit. The first monomer unit includes at least one selected from a group consisting of —O—Si—(R1)(R2)(R3), Si—(R1)(R2)(—O—)2, and Si—(R1)(—O—)3. the second monomer unit includes Si(—O—)4. The R1, R2 and R3 are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
According to some embodiments, the R1, R2 and R3 are independently selected from alkyl with not more than four carbon atoms.
According to some embodiments, at least one of the R1, R2 and R3 is selected from fluoroalkyl.
According to some embodiments, the tube is made of stainless steel; and the coating is bonded to the tube through a chemical bond of —O—.
According to some embodiments, a thickness of the coating is in the range of 0.1 μm to 2 μm.
According to some embodiments, a surface roughness of the coating is in the range of 2 nm to 100 nm.
According to some embodiments, a bonding force between the tube and the coating is at least 4 B under a cross-cut test.
An injection needle applied to transporting adhesive includes a tube and a coating. The coating is formed on the inner surface of the tube. The material of the coating comprises polysiloxane. The polysiloxane comprises a first monomer unit and a second monomer unit. The first monomer unit comprises at least one group selected from the group consisting of —O—Si—(R1)(R2)(R3), Si—(R1)(R2)(—O—)2, and Si—(R1)(—O—)3. The second monomer unit comprises Si(—O—)4. The R1, R2 and R3 groups are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl.
According to some embodiments, the R1, R2 and R3 are independently selected from alkyl with not more than four carbon atoms.
According to some embodiments, at least one group of the R1, R2 and R3 is selected from fluoroalkyl.
According to some embodiments, the tube is made of stainless steel; and the coating is bonded to the tube through a chemical bond of —O—.
According to some embodiments, a thickness of the coating is in the range of 0.1 μm to 2 μm.
According to some embodiments, a surface roughness of the coating is in the range of 2 nm to 100 nm.
According to some embodiments, a bonding force between the tube and the coating is at least 4 B under a cross-cut test.
A method for manufacturing a coating applied on an injection needle for transporting adhesive. The injection needle comprising a tube. The method comprises: applying a hydroxylation treatment on the tube to form hydroxyl groups on an inner surface of the tube; immersing the tube in a slurry; wherein the slurry comprises a first monomer and a second monomer, the first monomer is selected from a silane containing at least one alkoxy and at least one alkyl, and the second monomer is selected from a silicate ester; applying a leveling treatment on the slurry adhered to the inner surface of the tube; and curing the slurry to form the coating on the inner surface of the tube. The alkyl in the silane and the alkyl in the silicate ester are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl; the silane comprises at least one selected from the group consisting of monosilane and bisilane; the silicate ester comprises at least one selected from the group consisting of monosilate ester and bisilate ester.
According to some embodiments, the alkyl group in the silane and the alkyl group in the silicate are independently selected from alkyl with not more than four carbon atoms.
According to some embodiments, at least one of the alkyl in the silane and the alkyl in the silicate is selected from fluoroalkyl.
According to some embodiments, a material of the tube comprises stainless steel, and the step of applying a hydroxylation treatment on the tube comprises: applying a plasma treatment in an air atmosphere to form hydroxyl groups on the tube; wherein a power of a plasma treatment machine in the plasma treatment is in the range of 100 W to 1000 W, and a time period of the plasma treatment is in the range of 0.5 min to 10 min.
According to some embodiments, an angle for leveling treatment applied on the slurry is in the range of 45 degrees to 90 degrees. A time period of leveling treatment applied on the slurry is in the range of 0.1 h to 1 h. A temperature for curing the slurry is in the range of 70 degrees Celsius to 80 degrees Celsius. A time period for curing the slurry is in the range of 2 h to 6 h.
In the disclosure, the outermost surface of the coating is composed of alkyl. The alkyl has excellent chemical stability, and do not react with the adhesive, thus effectively increase the service life of the injection needle. The method for manufacturing the coating applied on the injection needle in the disclosure, the raw materials are silane and silicate, and these raw materials are easily available, which is beneficial to reduce production costs. The method for manufacturing the coating has low requirements for equipment. The coating can be mass-produced. The method for manufacturing the coating also reduces the preparation cost, the reaction temperature is low, and the plastic will not be affected.
BRIEF DESCRIPTION OF THE DRAWINGS
Implementations of the present disclosure will now be described, by way of example only, with reference to the attached figures.
FIG. 1 illustrates simplified cross-sectional side view of an injection needle, in accordance with some embodiments of the present disclosure.
FIG. 2 illustrates a flowchart of a method for manufacturing an injection needle, in accordance with some embodiments of the present disclosure.
 DETAILED DESCRIPTION
It will be appreciated that for simplicity and clarity of illustration, where appropriate, reference numerals have been repeated among the different figures to indicate corresponding or analogous elements. In addition, numerous specific details are set forth in order to provide a thorough understanding of the embodiments described herein. However, it will be understood by those of ordinary skill in the art that the embodiments described herein can be practiced without these specific details. In other instances, methods, procedures, and components have not been described in detail so as not to obscure the related relevant feature being described. Also, the description is not to be considered as limiting the scope of the embodiments described herein.
The term “comprising,” when utilized, means “including, but not necessarily limited to”; it specifically indicates open-ended inclusion or membership in the so-described combination, group, series, and the like. If no conflict, the following embodiments and features in the embodiments can be combined with each other.
In some embodiments illustrated in FIG. 1 , an injecting needle 100 is provided. The injecting needle 100 includes a coating 10 and a tube 20. The coating 10 is applied on an inner surface of the tube 20 for transporting an adhesive. The tube 20 is made of stainless steel. The coating 10 prevents the tube 20 from being blocked by the adhesive.
A diameter of the tube 20 is not limited. In some embodiments, the diameter of the tube 20 is small, such as needle-size; in some embodiments, the diameter of the tube 20 is large.
The coating 10 is made of polysiloxane. The polysiloxane includes a first monomer unit and a second monomer unit. The first monomer unit is at least one selected from the group consisting of —O—Si—(R1)(R2)(R3), Si—(R1)(R2)(—O—)2, and Si—(R1)(—O—)3. The second monomer unit contains Si(—O—)4.
The polysiloxane is formed by a polymerization of silane compound containing at least one consisting of the R1, R2, and R3.
The R1, R2 and R3 are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl. A chemical stability of the alkyl is high. During transport of the adhesive, the coating 10 does not react with the tube 20 or the adhesive, so as to prevent the adhesive from blocking the tube 20 and improve a service life of the injection needle 100.
The R1, R2 and R3 are independently selected from alkyl with not more than four carbon atoms. The alkyl is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.
At least one of the R1, R2 and R3 can be fluoroalkyl. That is, at least one hydrogen atom in the R1, R2 and R3 is replaced by a fluorine atom. The fluorine atom increases a wear resistance of the coating 10, thereby improving the service life of the injection needle 100.
The coating 10 is applied on the tube 20 after hydroxylation treatment, and the coating 10 is bonded to the tube 20 through a chemical bond of —O—, thus, a bonding force between the tube 20 and the coating 10 is strong. The bonding force between the tube 20 and the coating 10 is at least 4B under a cross-cut test.
A thickness of the coating 10 is about in the range of 0.1 μm to 2 μm. If the thickness of the coating 10 is too thick, the coating 10 will be hard to solidify, and the stress of the coating will be high. Small crack may appear on the coating due the high stress. The adhesive may stick on the surface with small crack, which will cause the tube 20 blocked by the sticking adhesive, which reduces the service life of the injection needle 100. If the thickness of the coating 10 is too thin, the coating 10 cannot fully cover the inner surface of the tube 20, due to the adhesive having higher binding force with the rough surface than with the smooth surface, the adhesive will stick on the surface without coating 10 to block the tube 20, which also reduces the service life of the injection needle 100.
A surface roughness of the coating 10 is about in the range of 2 nm to 100 nm.
According to some embodiments, a method for manufacturing the coating 10 inside a tube 20 is also provided. The coating applied on an injection needle 100 for transporting adhesive. The injection needle 100 includes the tube 20. The tube 20 is made of stainless steel.
In some embodiments illustrated in FIG. 2 , the method for manufacturing the injection needle 100 includes following steps.
Step S1: applying a hydroxylation treatment on the tube 20 to form hydroxyl groups on an inner surface of the tube 20.
The step S1 can be carried out by applying a plasma treatment in an air atmosphere to form hydroxyl groups on the tube 20. According to some embodiments, the plasma treatment is applied in oxygen atmosphere to quickly form the hydroxyl groups on the tube 20. The hydroxyl groups increase an electrical polarity of the tube 20, which is conducive to adhesion of the coating 10 and increases the bonding force between the tube 20 and the coating 10.
According to some embodiments, the tube 20 is combined with another tube which made of plastic. For example, a needle holder containing stainless steel can be placed at one end of a syringe made of plastic. A power of a plasma treatment machine in the plasma treatment is about in the range of 100 W to 1000 W, and a time period of the plasma treatment is about in the range of 0.5 min to 10 min. The power and the time period of the plasma treatment cannot be too high or too long, either one may cause the plastic deformed.
Step S2: immersing the tube 20 in a slurry. The slurry includes a first monomer and a second monomer. The first monomer is selected from silane containing at least one alkoxy and at least one alkyl, and the second monomer is selected from silicate ester.
The alkyl in the silane and the alkyl in the silicate ester are independently selected from the group consisting of substituted alkyl and unsubstituted alkyl. The silane includes at least one selected from the group consisting of monosilane and bisilane. The silicate ester includes at least one selected from the group consisting of monosilate ester and bisilate ester.
A formula of the silane may include, but is not limited to at least one of R4O—Si—(R1)(R2)(R3), R4O—Si—(R1)(R2)(—OR3), R4O—Si—(R1)(—OR2)(—OR3), (R1)(R2)(R3)—Si—O—Si—(R4)(R5)(R6), and (R1)(R2)(R3)—Si—R4—Si—(OR5)(R6)(R7).
A formula of the silicate ester can be selected from at least one of (R8O—)(R9O—)Si(—OR10)(—OR11), and (R8O)(R9O)(R10O)—Si—O—Si—(OR11)(OR12)(OR13).
The first monomer is cross-linked with the second monomer. Specifically, the alkoxy of the first monomer reacts to form a group of
Figure US11891536-20240206-C00001
The alkoxy of the second monomer reacts to form a group of
Figure US11891536-20240206-C00002
The group of
Figure US11891536-20240206-C00003
and the group of
Figure US11891536-20240206-C00004
are crosslinked to form a networked structure. The networked structure contains polysiloxane of at least one monomer unit of —O—Si—(R1)(R2)(R3), —O—Si—(R1)(R2)(—O—), —O—Si—(R1)(—O—)2, and —O—Si(—O—)3. The first alkyl connected to silicon in the first monomer is disposed on the outermost layer of the formed polysiloxane. The first alkyl is in contact with the adhesive in the tube 20. The adhesive is mostly a molecule containing a polar group, the first alkyl is alkyl, which is a non-polar molecular. The intermolecular force between the first alkyl and the binder is relatively weak. After the coating 10 is formed, the first alkyl provides toughness to the coating 10, and the first alkyl also provides non-stick properties between the finished coating 10 and the adhesive it carries. After the second monomer is hydrolyzed, a glass-like structure is formed, which provides the coating 10 with a smoothness similar to that of inorganic substances, thereby preventing the coating 10 and the adhesive from being strongly bonded and causing the tube 20 to be blocked. In a percentage content of the coating 10, the first monomer should not be too much, otherwise it will cause the coating 10 to be too elastic, which is not conducive to the transporting of adhesive. A percentage content of the second monomer should not be too much, otherwise it will cause the coating 10 to be too crisp or brittle, and then the coating 10 might crack due to internal stresses during the drying process.
It should be noted that the R1, R2, R3, R4, R5, R6, R7 in silane and the R8, R9, R10, R11, R12, R13 in the silicate esters all represent alkyl. In a same embodiment, the R1, R2, R3, R4, R5, R6, R7 and the R8, R9, R10, R11, R12, R13 may be the same or different. The R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and R13 merely distinguish between the first alkyl and the second alkyl in the silanes and the alkyl in the silicate esters.
According to some embodiments, the alkyl in the silane (including the first alkyl and the second alkyl) and the alkyl in the silicate are independently selected from alkyl with not more than four carbon atoms. Thus, the alkyl has small steric hindrance, which is beneficial to the reaction between the first monomer and the second monomer.
According to some embodiments, at least one of the alkyl in the silane (including the first alkyl and the second alkyl) and the alkyl in the silicate is selected from fluoroalkyl. After the first monomer reacts with the second monomer, the first alkyl is formed in the coating 10, and the fluoroalkyl increases a wear resistance and hydrophobicity of the coating 10, thereby increasing the service life of the injection needle 100. During the reaction process, the fluoroalkyl connected to oxygen increases the polarity of the first monomer and the second monomer, and is beneficial to the removal of the second alkyl and the alkyl in the second monomer, thereby facilitating the formation of a networked structure.
During a process of immersing the tube 20, ultrasonic treatment and vacuuming steps can also be added to promote uniform distribution of the slurry on the tube 20.
Further, the slurry may include at least one of film-forming agent, viscosity regulator, dispersant, leveling agent, catalyst, and activator.
A mass ratio of the film-forming agent in the slurry is about in the range of 1% to 15%. According to some embodiments, the mass ratio of the film-forming agent in the slurry is one of 2.5%, 5.6%, 8.0%, 11.5%, and 13.9%.
The film-forming agent is at least one selected from the group consisting of dimethylsilanol, polymethylsilanetriol, tetraethyl orthosilicate, methyltriethoxysilane, dimethyldiethylsilane, ethyltrimethoxysilane, ethane-1,2-diylbis(methylsilane), 3-(aminopropyl)triethoxysilane (KH550) and 3-methacryloxypropyltrimethoxysilane (KH570). The addition of the film-forming agent allows the slurry to quickly form film to form a coating 10.
According to some embodiments, the film-forming agent is at least two selected from the group consisting of Tetraethyl orthosilicate, methyltriethoxysilane, dimethyldiethylsilane, ethyltrimethoxysilane and ethane-1,2-diylbis(methylsilane). The selection of the film-forming agent, that is, the selection range of the first monomer and/or the second monomer.
A mass ratio of the viscosity regulator in the slurry is about in the range of 10% to 20%. According to some embodiments, the mass ratio of the viscosity regulator in the slurry is one of 12.3%, 14.2%, 16.0%, 17.8%, and 19.1%.
The viscosity regulator is at least one selected from the group consisting of ethyl acetate, isopropyl acetate, ethylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and dipropylene glycol ethyl ether acetate. The viscosity regulator adjusts the viscosity of the slurry.
According to some embodiments, the viscosity regulator is at least two selected from the group consisting of ethyl acetate, isopropyl acetate, di(propylene glycol) methyl ether acetate and dipropylene glycol methyl ether acetate.
A mass ratio of the dispersant in the slurry is about in the range of 1% to 9%. According to some embodiments, the mass ratio of the dispersant in the slurry is one of 2.5%, 3.6%, 5.6%, 7.0%, and 7.5%.
The dispersant is at least one selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, and isobutanol. The dispersant reduces a force between the components of the slurry and facilitates the dispersion and spreading of the slurry.
According to some embodiments, the dispersant is at least two selected from the group consisting of methanol, ethanol and isopropanol.
A mass ratio of the leveling agent in the slurry is about in the range of 55% to 90%. According to some embodiments, the mass ratio of the leveling agent in the slurry is one of 60%, 66%, 70%, 73%, and 85%.
The leveling agent is at least one selected from the group consisting of 2-methoxyethanol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, 1-ethoxy-2-propanol, and dipropylene glycol ethyl ether. The leveling agent reduces an interfacial tension of the slurry and facilitates infiltration between the slurry and the tube 20.
According to some embodiments, the leveling agent is at least two selected from the group consisting of diethylene glycol monomethyl ether, 1-methoxy-2-propanol, and 2-ethoxyethanol.
A mass ratio of the catalyst in the slurry is about in the range of 0.02% to 2%. According to some embodiments, the mass ratio of the catalyst in the slurry is one of 0.10%, 0.52%, 0.85%, 1.28%, and 1.67%.
The catalyst is at least one selected from the group consisting of formic acid, acetic acid, hydrochloric acid, and hydrofluoric acid. The catalyst accelerates the reaction of the first monomer and the second monomer.
A mass ratio of the activator in the slurry is about in the range of 0.5% to 5%. According to some embodiments, the mass ratio of the activator in the slurry is one of 0.8%, 1.5%, 2.8%, 3.6%, and 4.5%.
The activator is water. The activator hydrolyses the first monomer and the second monomer, so that a crosslinking reaction occurs.
Step S3: applying a leveling treatment on the slurry adhered to the inner surface of the tube 20, so that the surface roughness of the coating 10 is smoothed, which can be about in the range of 2 nm to 100 nm. During the transporting of the adhesive, the surface roughness of the coating 10 should not be too great, which would hinder a flow of the adhesive.
An angle for leveling treatment applied on the slurry is about in the range of 45 degrees to 90 degrees.
A time period of leveling treatment applied on the slurry is about in the range of 0.1 h to 1 h. According to some embodiments, the time period of the leveling treatment is one of 0.2 h, 0.4 h, 0.6 h, 0.8 h, and 0.9 h.
Step S4: curing the slurry to form the injection needle 100 with the coating 10 on the inner surface of the tube 20.
A temperature for curing the slurry is about in the range of 70 degrees Celsius to 80 degrees Celsius. According to some embodiments, the temperature is one of 72 degrees Celsius, 74 degrees Celsius, 76 degrees Celsius, and 78 degrees Celsius.
A time period for curing the slurry is about in the range of 2 h to 6 h. According to some embodiments, the time period is one of 2.6 h, 3.3 h, 4.2 h, 4.9 h, and 5.4 h.
Hereinafter, the disclosure will be described through specific embodiments. In the following embodiments, the material of the tube 20 contains stainless steel, and the tubes are all needles.
Example 1
A hydroxylated injection needle was immersed in the slurry including the first monomer and the second monomer. The first monomer was methyltriethoxysilane. The mass ratio of methyltriethoxysilane in the slurry was 0.3%. The second monomer was tetramethyl orthosilicate. The mass ratio of tetramethyl orthosilicate in the slurry was 5%.
The structural formula of methyltriethoxysilane was
Figure US11891536-20240206-C00005
The structural formula of tetramethyl orthosilicate was
Figure US11891536-20240206-C00006
After the slurry was leveled, the slurry was cured to form a coating on the inner surface of the injection needle.
After a contact angle test, the contact angle of the coating was 100 degrees. The injection needle with the coating continuously transports adhesive, and the service life of the injection needle was 38 h.
Example 2
A difference from the Example 1 was that the first monomer was triethoxyisobutylsilane, the mass ratio of triethoxyisobutylsilane in the slurry was 0.6%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 5% in Example 2.
The structural formula of triethoxyisobutylsilane was
Figure US11891536-20240206-C00007
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00008
The contact angle of the coating was 88 degrees. The service life of the injection needle was 46 h.
Other features are as in Example 1, and are not repeated here.
Example 3
A difference from the Example 1 was that the first monomer was propyltriethoxysilane, the mass ratio of propyltriethoxysilane in the slurry was 0.4%; and the second monomer was tetraisopropyl orthosilicate, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 8% in Example 3.
The structural formula of propyltriethoxysilane was
Figure US11891536-20240206-C00009
The structural formula of tetraisopropyl orthosilicate was
Figure US11891536-20240206-C00010
The contact angle of the coating was 84 degrees. The service life of the injection needle was 36 h.
Other features are as in Example 1, and are not repeated here.
Example 4
A difference from the Example 1 was that the first monomer was 1,2-bis(triethoxysilyl)ethane, the mass ratio of 1,2-bis(triethoxysilyl)ethane in the slurry was 0.5%; and the second monomer was tetrabutylorthosilicate, and the mass ratio of tetrabutylorthosilicate in the slurry was 7% in Example 4.
The structural formula of 1,2-bis(triethoxysilyl)ethane was
Figure US11891536-20240206-C00011
The structural formula of tetrabutylorthosilicate was
Figure US11891536-20240206-C00012
The contact angle of the coating was 79 degrees. The service life of the injection needle was 34 h.
Other features are as in Example 1, and are not repeated here.
Example 5
A difference from the Example 1 was that the first monomer was trimethoxy(propyl)silane, and the mass ratio of trimethoxy(propyl)silane in the slurry was 0.5%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 5% in Example 5.
The structural formula of trimethoxy(propyl)silane was
Figure US11891536-20240206-C00013
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00014
The contact angle of the coating was 87 degrees. The service life of the injection needle was 48 h.
Other features are as in Example 1, and are not repeated here.
Example 6
A difference from the Example 1 was that the first monomer was diethoxydimethylsilane, the mass ratio of diethoxydimethylsilane in the slurry was 0.7%; and the second monomer was tetraisopropyl orthosilicate, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 7% in Example 6.
The structural formula of diethoxydimethylsilane was
Figure US11891536-20240206-C00015
The structural formula of tetraisopropyl orthosilicate was
Figure US11891536-20240206-C00016
The contact angle of the coating was 75 degrees. The service life of the injection needle was 50 h.
Other features are as in Example 1, and are not repeated here.
Example 7
A difference from the Example 1 was that the first monomer was methoxy(trimethyl)silane, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.2%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 4% in Example 7.
The structural formula of methoxy(trimethyl)silane was
Figure US11891536-20240206-C00017
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00018
The contact angle of the coating was 92 degrees. The service life of the injection needle was 46 h.
Other features are as in Example 1, and are not repeated here.
Example 8
A difference from the Example 1 was that the first monomer was methyltriethoxysilane and methoxy(trimethyl)silane, the mass ratio of methyltriethoxysilane in the slurry was 1%, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.5%; and the second monomer was tetraethyl orthosilicate and tetramethyl orthosilicate, the mass ratio of tetraethyl orthosilicate in the slurry was 3%, the mass ratio of tetramethyl orthosilicate in the slurry was 3% in Example 8.
The structural formula of methyltriethoxysilane was
Figure US11891536-20240206-C00019
The structural formula of methoxy(trimethyl)silane was
Figure US11891536-20240206-C00020
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00021
The structural formula of tetramethyl orthosilicate was
Figure US11891536-20240206-C00022
The contact angle of the coating was 106 degrees. The service life of the injection needle was 40 h.
Other features are as in Example 1, and are not repeated here.
Example 9
A difference from the Example 1 was that the first monomer was isobutyltriethoxysilane and diethoxydimethylsilane, the mass ratio of isobutyltriethoxysilane in the slurry was 0.5%, the mass ratio of diethoxydimethylsilane in the slurry was 1%; and the second monomer was tetraethyl orthosilicate and tetraisopropyl orthosilicate, the mass ratio of tetraethyl orthosilicate in the slurry was 4%, and the mass ratio of tetraisopropyl orthosilicate in the slurry was 1% in Example 9.
The structural formula of isobutyltriethoxysilane was
Figure US11891536-20240206-C00023
The structural formula of diethoxydimethylsilane was
Figure US11891536-20240206-C00024
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00025
The structural formula of tetraisopropyl orthosilicate was
Figure US11891536-20240206-C00026
The contact angle of the coating was 98 degrees. The service life of the injection needle was 50 h.
Other features are as in Example 1, and are not repeated here.
Example 10
A difference from the Example 1 was that the first monomer was methyltriethoxysilane, methoxy(trimethyl)silane and trimethoxy(propyl)silane, the mass ratio of methyltriethoxysilane in the slurry was 0.5%, the mass ratio of methoxy(trimethyl)silane in the slurry was 0.5%, and the mass ratio of trimethoxy(propyl)silane in the slurry was 1%; and the second monomer was tetraethyl orthosilicate, and the mass ratio of tetraethyl orthosilicate in the slurry was 6% in Example 10.
The structural formula of methyltriethoxysilane was
Figure US11891536-20240206-C00027
The structural formula of methoxy(trimethyl)silane was
Figure US11891536-20240206-C00028
The structural formula of trimethoxy(propyl)silane was
Figure US11891536-20240206-C00029
The structural formula of tetraethyl orthosilicate was
Figure US11891536-20240206-C00030
The contact angle of the coating was 90. The service life of the injection needle was 54 h.
Other features are as in Example 1, and are not repeated here.
Comparative Example 1
A difference from the Example 1 was that the monomer was (3-glycidyloxypropyl)trimethoxysilane, the mass ratio of (3-glycidyloxypropyl)trimethoxysilane in the slurry was 5% in Comparative Example 1.
The structural formula of (3-glycidyloxypropyl)trimethoxysilane was
Figure US11891536-20240206-C00031
The contact angle of the coating was 60 degrees. The service life of the injection needle was 5 h.
Other features are as in Example 1, and are not repeated here.
Comparative Example 2
A difference from the Example 1 was that the monomer was (aminopropyl)triethoxysilane, the mass ratio of (aminopropyl)triethoxysilane in the slurry was 6% Comparative Example 2.
The structural formula of (aminopropyl)triethoxysilane was
Figure US11891536-20240206-C00032
The contact angle of the coating was 70 degrees. The service life of the injection needle was 5 h.
Other features are as in Example 1, and are not repeated here.
Comparative Example 3
A difference from the Example 1 was that the monomer was vinyltrimethoxysilane, the mass ratio of vinyltrimethoxysilane in the slurry was 3% Comparative Example 3.
The structural formula of vinyltrimethoxysilane was
Figure US11891536-20240206-C00033
The contact angle of the coating was 65 degrees. The service life of the injection needle was 6 h.
Other features are as in Example 1, and are not repeated here.
Referring to Table 1 for the main different conditions and test results of Examples (short to Ex) 1 to 10 and Comparative Examples (short to Co-ex) 1 to 3.
TABLE 1
first monomer second monomer contact angle service life
name mass ratio name mass ratio (degrees) (h)
Ex 1 methyltriethoxysilane 0.3% tetramethyl orthosilicate 5% 100 38
Ex 2 triethoxyisobutylsilane 0.6% tetraethyl orthosilicate 5% 88 46
Ex 3 propyltriethoxysilane 0.4% tetraisopropyl orthosilicate 8% 84 36
Ex 4 1,2-bis(triethoxysilyl)ethane 0.5% tetrabutylorthosilicate 7% 79 34
Ex 5 trimethoxy(propyl)silane 0.5% tetraethyl orthosilicate 5% 87 48
Ex 6 diethoxydimethylsilane 0.7% tetraisopropyl orthosilicate 7% 75 50
Ex 7 methoxy(trimethyl)silane 0.2% tetraethyl orthosilicate 4% 92 46
Ex 8 methyltriethoxysilane, 1%, 0.5% tetraethyl orthosilicate, 3%, 3% 106 40
methoxy(trimethyl)silane tetramethyl orthosilicate
Ex 9 isobutyltriethoxysilane, 0.5%, 1%   tetraethyl orthosilicate, 4%, 1% 98 50
diethoxydimethylsilane tetraisopropyl orthosilicate
Ex 10 methyltriethoxysilane, 0.5%, 0.5%, tetraethyl orthosilicate 6% 90 54
methoxy(trimethyl)silane, 1%
trimethoxy(propyl)silane
Co-ex 1 (3-glycidyloxypropyl)trimethoxysilane   5% without without 60 5
Co-ex 2 (aminopropyl)triethoxysilane   6% without without 70 5
Co-ex 3 vinyltrimethoxysilane   3% without without 65 6
Comparing the test results of Examples 1 to 10 and Comparative Examples 1 to 3 clearly shows that the contact angles of the injection needles with the coating made in Examples 1 to 10 are larger than those of Comparative Examples 1 to 3, which prevents the adhesive from sticking to the tube. Compared with Comparative Examples 1 to 3, the service life of the injection needles made in Examples 1 to 10 was greatly improved, and service life was 7 to 10 times that of Comparative Examples 1 to 3.
After the monomers provided in Comparative Examples 1 to 3 form the coating, they contain epoxy groups
Figure US11891536-20240206-C00034
amine groups (—NH2), vinyl groups (—CH═CH2) and other active groups, which readily react with the oxygen-containing functional groups in the adhesive, and the adhesive blocks the tube after a period of use. After the monomers provided in Examples 1 to 10 form the coating, the surface of the coating was alkyl with good chemical stability, and alkyl does not react with the adhesive, thereby effectively increasing the service life of the injection needle.
In the coating provided in the disclosure, the outermost surface of the coating is composed of alkyl. The alkyl has excellent chemical stability, and do not react with the adhesive, thus effectively increase the service life of the injection needle. The method for manufacturing the coating in the disclosure, the raw materials are silane and silicate, and these raw materials are easily available, which is beneficial to reduce production costs. The method for manufacturing the coating has low requirements for equipment. The coating can be mass-produced. The method for manufacturing the coating also reduces the preparation cost, the reaction temperature is low, and the plastic will not be affected.
It is to be understood, even though information and advantages of the present embodiments have been set forth in the foregoing description, together with details of the structures and functions of the present embodiments, the disclosure is illustrative only; changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the present embodiments to the full extent indicated by the plain meaning of the terms in which the appended claims are expressed.

Claims (19)

What is claimed is:
1. A method for manufacturing a coating applied on an injection needle for transporting adhesive, the injection needle comprising a tube, the method comprising:
applying a hydroxylation treatment on the tube to form hydroxyl groups on an inner surface of the tube;
immersing the tube in a slurry; wherein the slurry comprises a first monomer and a second monomer, the first monomer is selected from a silane containing at least one alkoxy and at least one alkyl, and the second monomer is selected from a silicate ester;
applying a leveling treatment on the slurry adhered to the inner surface of the tube; and
curing the slurry to form the coating on the inner surface of the tube;
wherein, the alkyl in the silane and a alkyl in the silicate ester are independently selected from a group consisting of substituted alkyl and unsubstituted alkyl; the silane comprises at least one selected from a group consisting of monosilane and bisilane; the silicate ester comprises at least one selected from a group consisting of monosilate ester and bisilate ester;
an angle for the leveling treatment applied on the slurry is in a range of 45 degrees to 90 degrees; a time period of the leveling treatment applied on the slurry is in a range of 0.1 h to 1 h; a temperature for curing the slurry is in a range of 70 degrees Celsius to 80 degrees Celsius; and a time period for curing the slurry is in a range of 2 h to 6 h.
2. The method of claim 1, wherein an alkyl group in the silane and an alkyl group in the silicate are independently selected from alkyl with not more than four carbon atoms.
3. The method of claim 2, wherein at least one of the alkyl in the silane and the alkyl in the silicate is selected from fluoroalkyl.
4. The method of claim 1, wherein a material of the tube comprises stainless steel, applying the hydroxylation treatment on the tube comprises:
applying a plasma treatment in an air atmosphere to form hydroxyl groups on the tube; wherein a power of a plasma treatment machine in the plasma treatment is in a range of 100 W to 1000 W, and a time period of the plasma treatment is in a range of 0.5 min to 10 min.
5. The method of claim 1, wherein the slurry comprises at least one selected from a group consisting of film-forming agent, viscosity regulator, dispersant, leveling agent, catalyst, and activator.
6. The method of claim 5, wherein a mass ratio of the film-forming agent in the slurry is in a range of 1% to 15%.
7. The method of claim 5, wherein the film-forming agent is at least one selected from a group consisting of dimethylsilanol, polymethylsilanetriol, tetraethyl orthosilicate, methyltriethoxysilane, dimethyldi ethyl silane, ethyltrimethoxysilane, ethane-1,2-diylbis(methylsilane), 3-(aminopropyl)triethoxysilane, and 3-methacryloxypropyltrimethoxysilane.
8. The method of claim 7, wherein the film-forming agent is at least two selected from a group consisting of tetraethyl orthosilicate, methyltriethoxysilane, dimethyldiethylsilane, ethyltrimethoxysilane and ethane-1,2-diylbis(methylsilane).
9. The method of claim 5, wherein a mass ratio of the viscosity regulator in the slurry is in a range of 10% to 20%.
10. The method of claim 5, wherein the viscosity regulator is at least one selected from a group consisting of ethyl acetate, isopropyl acetate, ethylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and dipropylene glycol ethyl ether acetate.
11. The method of claim 10, wherein the viscosity regulator is at least two selected from a group consisting of ethyl acetate, isopropyl acetate, di(propylene glycol) methyl ether acetate, and dipropylene glycol methyl ether acetate.
12. The method of claim 5, wherein a mass ratio of the dispersant in the slurry is in a range of 1% to 9%.
13. The method of claim 5, wherein the dispersant is selected at least one from a group consisting of methanol, ethanol, isopropanol, n-butanol, and isobutanol.
14. The method of claim 13, wherein the dispersant is at least two selected from a group consisting of methanol, ethanol and isopropanol.
15. The method of claim 5, wherein a mass ratio of the leveling agent in the slurry is in a range of 55% to 90%.
16. The method of claim 5, wherein the leveling agent is at least one selected from a group consisting of 2-methoxyethanol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, 1-ethoxy-2-propanol, and dipropylene glycol ethyl ether.
17. The method of claim 5, wherein a mass ratio of the catalyst in the slurry is in a range of 0.02% to 2%.
18. The method of claim 5, wherein the catalyst is at least one selected from a group consisting of formic acid, acetic acid, hydrochloric acid, and hydrofluoric acid.
19. The method of claim 5, wherein a mass ratio of the activator in the slurry is in a range of 0.5% to 5%.
US17/533,407 2020-12-02 2021-11-23 Coating, injection needle and method for manufacturing the same Active US11891536B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011402400.7 2020-12-02
CN202011402400.7A CN112742686A (en) 2020-12-02 2020-12-02 Coating and method for producing coating

Publications (2)

Publication Number Publication Date
US20220169891A1 US20220169891A1 (en) 2022-06-02
US11891536B2 true US11891536B2 (en) 2024-02-06

Family

ID=75649056

Family Applications (1)

Application Number Title Priority Date Filing Date
US17/533,407 Active US11891536B2 (en) 2020-12-02 2021-11-23 Coating, injection needle and method for manufacturing the same

Country Status (2)

Country Link
US (1) US11891536B2 (en)
CN (1) CN112742686A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005067992A1 (en) * 2004-01-19 2005-07-28 University Of South Australia Bioactive coating of biomedical implants
KR20120111664A (en) * 2011-04-01 2012-10-10 인하대학교 산학협력단 Hydrophobic silica coating layer, and forming method of the same
CN103205201A (en) 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof
CN108299913A (en) 2016-10-08 2018-07-20 深圳宝顺美科技有限公司 A kind of hydrophobic coating material and hydrophobic coating
CN109762464A (en) 2019-01-28 2019-05-17 新辉（中国）新材料有限公司 Hydrophobic coating material of high-hardness high-light pool degree of room temperature curing and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1325416C (en) * 2005-10-14 2007-07-11 浙江大学 Glass hydrophobic film coating liuqid
CN101280155B (en) * 2007-04-02 2010-08-18 中国科学院化学研究所 Self-cleaning film and preparation thereof
CN104059400B (en) * 2014-06-25 2016-06-22 上海宜瓷龙新材料股份有限公司 A kind of coating for printing figuratum tableware and implementation thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005067992A1 (en) * 2004-01-19 2005-07-28 University Of South Australia Bioactive coating of biomedical implants
KR20120111664A (en) * 2011-04-01 2012-10-10 인하대학교 산학협력단 Hydrophobic silica coating layer, and forming method of the same
CN103205201A (en) 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof
CN108299913A (en) 2016-10-08 2018-07-20 深圳宝顺美科技有限公司 A kind of hydrophobic coating material and hydrophobic coating
CN109762464A (en) 2019-01-28 2019-05-17 新辉（中国）新材料有限公司 Hydrophobic coating material of high-hardness high-light pool degree of room temperature curing and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R1, ALIAS for AKTA pure, 2014, Spark Holland, pp. 1-6 (Year: 2014). *

Also Published As

Publication number Publication date
US20220169891A1 (en) 2022-06-02
CN112742686A (en) 2021-05-04

Similar Documents

Publication Publication Date Title
KR100845403B1 (en) Manufacturing method for organic-inorganic hybrid coating solution for ambient thermal polymerization
EP2591060B1 (en) Coating systems capable of forming ambiently cured highly durable hydrophobic coatings on substrates
US6228921B1 (en) Process for the production of compounds based on silanes containing epoxy groups
TWI691505B (en) Liquid composition for film formation and manufacturing method thereof
JP2016513156A5 (en)
JP2010503519A (en) Silane coating material and method for producing a silane coating
JP5900512B2 (en) Method for producing gas barrier film
JP2002528590A (en) Composition for providing an abrasion resistant coating on a substrate having improved adhesion and improved resistance to crack formation
JP2009040991A (en) Coating liquid composition, heat-resistant coating film and method for forming the film
US20020068793A1 (en) Boron- and/or aluminum-containing mixtures, hybrid materials, and coatings
KR20130017057A (en) Transparent optical hybrid material
JP2002212503A (en) Film-forming composition, method for producing the composition, method for forming porous film, and the porous film
CN1155672C (en) Coating compositions with a base consisting of silanes contg. epoxide groups
US20190185708A1 (en) Crack-resistant silicon-based planarizing compositions, methods and films
US11891536B2 (en) Coating, injection needle and method for manufacturing the same
KR101176954B1 (en) Plastic-organic/inorganic hybrid adhesive film and preparation method thereof
JP6753765B2 (en) Liquid composition for film formation
JP2008255143A (en) Silicon fine particles, method for producing the same, solar cell by using the same, and method for producing solar cell
JP4324775B2 (en) Coating composition and structure for undercoating containing photocatalyst coating film
JP4893103B2 (en) Coating liquid for coating film formation, coating film therefor, and coating film forming method
US9308551B2 (en) Surface treatment method for substrate and housing manufactured by the same
JP2012116969A (en) Coating composition
US7097704B1 (en) Tintable abrasion resistant coating composition and methods of making and using same
US8623127B2 (en) Metal mold, process for manufacturing the same, and molded article produced using the mold
JP2002080784A (en) Releasable and nontacky coating composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: SHENZHENSHI YUZHAN PRECISION TECHNOLOGY CO., LTD., CHINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WANG, WEI;XU, BO-LING;FU, XIAO-QING;AND OTHERS;REEL/FRAME:058193/0292

Effective date: 20210809

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

AS Assignment

Owner name: FULIAN YUZHAN PRECISION TECHNOLOGY CO.,LTD, CHINA

Free format text: CHANGE OF NAME;ASSIGNOR:SHENZHENSHI YUZHAN PRECISION TECHNOLOGY CO., LTD.;REEL/FRAME:060158/0203

Effective date: 20220302

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE